Vinyl chloride resin compositions containing an alkyl nu, nu-bis (2-cyanoethyl) carboxamate as a plasticizer



United States Patent VINYL CHLORIDE RESIN COMPOSITIONS CON- TAININ G AN ALKYL N,N-BIS (Z-CYANOETHYL) CARBOXAMATE AS A PLAS'IICIZER Theodore E. Mullen, South Charleston, W. Va., assignor g) IiTKnion Carbide Corporation, a corporation of New No Drawing. Filed July 31, 1953, Ser. No. 371,723

9 Claims. (Cl. 260-313) This invention relates to plasticized compositions and has for an object the provision of an improved type of plasticized composition. More particularly, this invention is directed to a polyvinyl resin composition containing as a plasticizer an alkyl N,N-bis(2-cyanoethyl)- carboxamate.

As a rule, polyvinyl resins are generally too hard and rigid to be used for many purposes without a modifier, commonly referred to as a plasticizer. It is usually necessary to add a plasticizer to make the resins soft, pliable and capable of being formed into strong pliable sheets or films. It is also necessary that the plasticized resin composition have excellent heat stability, suppleness and elasticity. In order for a material to act as a plasticizer, it is necessary that it be compatible with the resin and not exude or sweat out leaving the resin unplasticized.

The plasticizers of my invention are useful in plasticizing the polyvinyl resins such as, for example, the vinyl chloride-vinyl acetate copolymer resins, the vinyl chloride-vinyl acetate-vinyl alcohol resins, the vinyl acetate resins, the vinyl chloride resins, the ter-polymer of vinyl chloride-vinyl acetate and maleic acid, the ter-polymers of vinyl chloride-acrylonitrile and vinyl acetate and the vinyl chloride-acrylonitrile resins.

A more specific aspect of my invention comprises the plasticized compositions of vinyl chloride-acrylonitrile copolymer resins.

Acrylonitrile polymers are, as a class, extremely difiicult to fabricate by processes involving resin flow at elevated temperatures. They are not amenable to plasticization, and their troublesome solubility characteristics have often discouraged the development of solution processes. Thus, the utility of the acrylonitrile polymers was limited to the field of fibers but now the new plasticized composition of my invention permits the use of acrylonitrile polymers in such fields as coatings, molded articles, films, and calendered sheets, etc.

I have now discovered that compounds having the following structural formula represent a class of compounds which are excellent plasticizers for polyvinyl resins and more particularly the acrylonitrile polymers and copolymers:

wherein R represents a divalent, aliphatic hydrocarbon radical and R represents an alkyl radical.

2,938,878 Patented May 31, 1960 I have also discovered that the plasticizers defined by the structural formula above are compatible with /2 second nitrocellulose, cellulose acetate butyrate, ethyl cellulose, and cellulose acetate.

The plasticizers of my invention impart excellent flexibility characteristics to the final product, and, in addition, the final product does not show cloudiness or exudation, even after several months of aging, but, perhaps the most important advantages in employing my new plasticizer are low volatility, and utility in certain applications requiring flexibility at low temperatures. Thus, additional uses of the new plasticized compositions in cloth coatings, paper coatings, metal coatings, wire coatings, calendered sheets, and molded articles are now possible.

The improved types of plasticized compositions of matter comprising my invention are directed to a polyvinyl resin composition plasticized with an alkyl N,N-bis(2- cyanoethyl) carboxamate, and, more particularly, the novel compositions comprise an acrylonitrile resin plasticized with a compound having the formula:

wherein R represents a divalent, aliphatic hydrocarbon radical and R represents an alkyl radical. A'preferred species of my invention is a composition of matter comprising an acrylonitrile copolymer resin plasticized with a compound having the formula:

wherein R represents a divalent, aliphatic hydrocarbon radical and R represents an alkyl radical.

More particularly, the plasticized acrylonitrile copolymer compositions comprising my invention are directed to compositions comprising acrylonitrile-vinyl chloride copolymers plasticized with a compound having the formula:

wherein R represents a divalent, aliphatic hydrocarbon radical and R represents an alkyl radical.

The percentage of vinyl chloride in the acrylonitrilevinyl chloride copolymer resin can vary within a wide range, usually 0 to but a preferred range is a composition of a vinyl chloride-acrylonitrile copolymer resin containing an amount of vinyl chloride in the range of from about 25 to 100%. Thus, a further embodiment of my invention comprises a vinyl chloride-acrylonitrile copolymer resin containing an amount of vinyl chloride a 3 in the range of from about 25 to 100% plasticized with a compound having the formula:

wherein R represents a divalent, aliphatic hydrocarbon radical and R'represents an alkyl radical.

The plasticizers which form a part of my invention may be readily prepared by reacting a cyclic anhydride of a dibasic acid with di(2-cyanoethyl) amine and esterifying the resulting N,N-bis(2-cyanoethyl)carboxamic acids with a suitable alcohol in accordance with the following equations:

' (I'll-0H t (II) wherein R represents a divalent aliphatic hydrocarbon radicals and R represents the radical derived from the alcohol in the esterification reaction.

The preferred plasticizers which form a part of this invention include, for example:

Methyl N,N-bis (Z-cyanoethyl) succinamate Ethyl N,N-bis (Z-cyanoethyl) succinamate Butyl N,N-bis (Z-cyanoethyl) succinamate Isopropyl N,N-bis(2-cyanoethyl succinamate Z-ethylbutyl N,N-bis(2-cyanoethyl)succinamate Z-ethylhexyl N,N-bis 2-cyanoethyl) succinamate Ethyl N,N-bis (2-cyano ethyl) fumaramate Allyl N,N-bis 2-cyanoethyl) succinamate Butyl N,N-bis (Z-cyano ethyl) glutaramate Various plasticizers, including many not included in this invention, were tested with the vinyl resins by the use of a simple screening test, i.e., the plasticizers were tested with various resins and those compounds which were observed and found not to impart flexibility to the composition, or that were not compatible with the resin, were screened out. acetone were placed into two different beakers. cient plasticizer to be tested was stirred into the solution to give a resin to plasticizer ratio of 1 to l in one beaker and 2' to 1 in the other beaker. The mixtures were 7 left to dry overnight. The resulting films or plaques were removed and allowed to air dry for one or two days longer. The two plaques were cut in half and one-half of each plaque was baked for one hour at 300 F., since baking in this manner tends to accentuate incompatibilities. The four plaques were then observed for flexibility, cloudiness and signs of exudation. These ratings were repeated at one week, one month and after three to six months. From these observations each compound was rated as to effectiveness (ability to impart flexibility to the-composition) and as to compatibility with the resin (freedom from cloudiness or exudation). More particularly, I have prepared compositions of vinyl chloride-acrylonitrilc resin and theplasticizers of my invention and tested them in the manner set forth above. 7 p i w The fused plaques described above may also be made by forming a plastisol or an organosol rather'than castingthe plaques from a solution of acetone as describe Portions of vinyl resin in,

Suifi v Rating V v V I v Effectiveness 10=very flexible; 0=stifl5 Compatibility", 10=no cloudiness, no exu- I r dation; 8 =slight cloudiness. or exudation, etc.-

- SCREENING TESTS Table 1 V Ratin Name Remarks Eflective- Compatlness. bility Dl-(2-ethylhexyl)phthalate.. 1 1 Cloudy-bad sweat'out. Tri-(Z-ethylhexyl) phosphate. 0 0 Do. Triethylene glycol di(2-ethyl- 0 0 Do.

hexoate). Polyethylene glycol di(2-eth- 0 0 Do.

ylhexoat 2,2'- (2-ethylhexamido) dieth- 1 1 Do.

yl-di-(Zethylhexoate). Dl-(z-ethylhexyl) tetrahydro- 0 0 Do."

phthalate. I Tetrabutylthiod1succiuate O .3 Cleudy-not eflec t ya. I Di-(2-ethylhexyl) adlpate. l. 0 Cloudy-barlsweat out. Trl-cresyl Phosphate 0 5 Not efiectlve. Di-(tetrahydroiurfuryl 9 9 Sweats out on long phthalate. ageing or exposure to light. Santicizer 8" 9 10 Very volatile. "Santlcizer 9" 8 6 Cloudy-not efiect ve. Santlclzer 130" 9 8 Exudes. Santiclzer131"- 9 8 Do. Santiclzer 8. 9 7 Do. Santicizer 1H-. 8 10 Not efiective and too volatile.

4 above. The method of preparing the fused plaque does not have any efieot on ultimate utility of the plasticized composition.

I have compared the plasticizers of the present invention with some of the plasticizers on the market with samples of various resins in an eifort to evaluate the plasticizers for effectiveness and compatibility with the resin. In order to emphasize and point out more clearly the significance of my invention I have prepared tables comparing some of the better plasticizers on the market and the plasticizers of the present invention rating them on their ability to produce flexible compositions with a 60-40 vinyl chloride-acrylonitrile copolymer resin and also rating them on their compatibility with the resin.

Some of the more desirable plasticizers available on the market include: V

Other plasticizers available on the open market include plasticizers sold under the trademark Santicizer which include:

Santicizer 8=A mixture of ortho and para toluene ethyl sulfonamides Santicizer 9=A mixture of ortho and para toluene sulfonamides.

Santicizer =Nisopropyl benzene sulfonamide Santicizer 131=Mixed N-isopropyl benzene sulfonamide and N-isopropyl toluene sulfonamide Santicizer 3=N-ethyl-p-toluene sulfonamide I Santicizerr IH=Cyclohexyl-p-toluene sulfonamide Usingan' acetone solution, films of 60-40 vinyl chloride-acrylonitrile copolymerresin and the test compound were prepared in the manner described above and then visually examined for:

bility (fix). Ratings used were good (G), fair (F), and

vvpoontP) for .clarity and flexibility, whereas the exuda- .l was we as modem wit *9 the 9 renewed and each .li high chloride resins (SS-100%) usually dissolved in 'combmatlon of resin and plastlcizer was rated as to comcyclohexanone, the medium. chloride resins V(50 85%) fipatibility P andrefiectivefless Plasticizingeacr usually dissolved in acetone and the lower chloride resins i tion. Theratingbasiswas 10,;20Qd, r0- -:poor. dissolved in dimethylformamide and eflfectiveness testqwith resins of high vinyl chloride content. 4

w W Table V EFFECT OF 'VINYL CHLORIDE CONTENT OF RESIN ON PLASTICIZED COMPOSITION 4:1 Resin to Plast. 1:1 Resin to Plast.

Percent Red. Vise. Weeks VOL. asp/.2 Aged 7 Air Dried 1 hr. at 300 F. Air Dried 1 hr. at 300 F. Rating 7 Cl FIX Cl EXLI FIX C1 FIX Cl Em FIX C0 E o G V B G G B G G B G G B G 98.8 1.41 NB.-- 1 G- B G G B G G B G G B G I, '4 G 13 G: G B G G B G G B G 6 9 v 0 G B G G B G G B G G B G r 100 "1.....- 0.98 NB.-- l 1 B G- G B F G B G G B G 4 G B G G B F G B G G B G 6 9 The following Table VI shows a comparison of various alkyl N,N -'bis(Z-cyanoethyDsuccinamates in compositions of various vinyl chloride and acrylonitrile contents, as to their eifectiveness and compatibility:

I ofthe resins used in Table IV are oopolyn ers of .vinyl chloride and acrylonitrilemade usually by emulsion polymerization, whereas Table V illustrates compatibility Table VI 4 to 1 Resin to Plast. etc 1 Resin to Blast. 1 to 1 Resin to Pleat. w Rating 7 a Aged 7 Air Dried 1 hr. at 300 F. 'Air Dried 1 hr. at 300 F. Air Dried '1 hr. 811300, F.

-7 o1 Exu P1: 01 Exu Fix 01 Exu Fl: 01 Exu Fix o1 Exu Fl: 01 Exu Fix Co E Resin: 32% vinyl chloride. Plasticizer: Methyl N,N-bis(2-cyanoethyl) succinamate I N ..'...J G N G N G G G" G N G 51 G G N G V G N G G N G N o G N G G 7N G G B G a 10 gjiil jlllil Resin: 45% vmyiomsflas; Ebenezer: Methyl N,N-bis (Z-eyauoethyl) succlne mate N G G N G G 0 N G G N G N o G N G o N o G 'N G N G G G G N G 10 10 Resin: 94% Vinyl Chloride: Plastieizen- Mmyi NN-bts z-e anoem lysuccinsmate Resin: 100% Vinyl Qhloride lflasticizer; Methyllfl'dfI-bis(2-cyanoethyl) suceinamate n G P B F" P B G P B P B 0 P B Fr 7 1 P B G P B P z B G P B P P B e G P B P 2 2 .Resin: 100% Vinyl Chloride. Plasticizer; Z-EthylhexylN,N-bis(2-cyenoethyl)sueciiiamate N G G s1 G- G N G G 51 G G 'N' G "'G' s1 G N G G N G N o G 7 s1 F G s1 G G B G st G G N F G G7,, G B7. G G m: G MGM G 8 9 if :1: Resin: Polyam-ylonltrilel l lasticiieri-MethylNN-lns t2-oyanoethyllsueeina nate10150 1) G B F G N P G G G G P G G V P o G P G G P t G N P G G P G G P G U G PVWGW .G- P s 0 9 7 As can be seen from the above Tables V and VI;

alkyl esters of N,N-bis-(2-cyanoethyl)succinamic acids assesses the Table VII with a butyl N,Nbis(2-cyanoethyl)succinamate plasticizer in selectedrratios of resin to plasticizer.

to 1 Resin to Plast.

4 2 to 1 Resin to Plast.

Wks. i Aged Air Dried 1 hr. at 300 F. Air Dried 1 hr. at 300 F. Rating Cl. Exu Flx C1 Exu Flx O1 Exu Flx C1 Exu F13 Co E vlnylidene chloride (79%) and acrylonltrlle, used at 20% in methyl ethyl ketone,

G F N G P N G P N G G F N G P N G P N G G F N G P N G P N G 10 10 Resin: A consecutive polymer of vinyl acetate on acrylonltrile, 40% acrylonitrile, nsp/.2-=1265 in dlmethyliormamide, used at 10% in toluene.

s1 G o N G P N N G G N G N G G N G G N 1.170 asp/.2 in dlmethylformamlde N N N N N N QQQ G G G eam ZZZ

Resin: Copolymer of acrylonitrile and styre 0 G N G G N P 1 G N G G N P 4 G N G G N P 9 G N P G N P 10 10 Table VIII EFFECT OF AORYLONI'IRILE GONTENT ON PLASTICIZED COMPOSITION 2:1 Resin to Plast. 1:1 Resin to Plast.

Wks. Aged Air Dried 1 hr. at 300 F. Air Dried 1 hr. at 300 F. Rating 01 E'xu Fl: 01 Exu Flx C1 Exu Flx Cl Exu Flx Co E Resin: Copolymer o! vinylldene chloride (53.4%) and acrylonltrile, 1.73 map/.2 in cyclohexanone used at 10% in dimethylformamlde.

N G .G N G G N G G N G N G G N G G N G G N G N G G N G G- N G G N G 10 10+ Resin Oopolymer oi vinylldene chloride (40.8%) and aerylonltrile, 1.91 nsp/.2 1n dimethylformamide, used at 15% in dimethylformamide.

N G- G B G- G N G G B G N G- G 81 G- G N G G S1 G N G- G B G- G N G G S1 G 7 10- are compatible with polyvinyl resins of 0-100% vinyl Morepart'icula'rly, it can be readily seen that the particular alkyl succinamates are compatible with vinylchloride-acrylonitrile resins of 0 to 100% vinyl chloride.

chloride.

The following Tables VII and VHI will show the "suits of tests of various acrylonitrile containing resins chanieal, and electrical resistivities. I have found that the compatibility of compositions of resin and plasticizer is not substantially affected when a ratio of resin to plastiei zer; of 1:1 is used. Naturally the type of plasticizer general ratios of resin to plasticizcr of 1:1 to 2:1 and even as high as 10:1 have proved entirely satisfactory.

12 films were quite strong and flexible. The following properties were determined on the thin films:

A preferred range of the plasticizer to the resin is an 5 gaking sltlensiiteh reree t Igra rennt lg e ent v1 m em ram 011 8 on 8 61' X- 8 amount of plasticizer of from about to 60% by weight, 0 f, at Bfeak I Extraction, "action I Y based on the total composition. s Arfurther embodiment of my invention comprises a jff; 175 800V 125 vinyl chloride-acrylonitrile copolymer resin containing an, 200 1300 21s I amount, of from about 5% to 60% by weight, based on 1323 3 the total composition, of a plasticizer having the formula: 23 3 23 radical and R represents an alkyl radical. V

A specific embodiment of my invention comprises compositions consisting of vinyl chloride-acrylonitrile copolymerresins having a vinyl chloride content in the range of from about,25 to 100% "and containing an amount of from about 5% to 60% by weight, based on the total composition, of a plasticizer having the formula:

0 30 l /mNwfiuJncN)i v, Plastisol Milled Sheet 4 R Plaque u as Tensile Strength, p.s.i 1825 1950 o I Elongation, Percent 280 360 Load at 100% Elongation, p.s.i 825 600 iQISTig StifinetsgrM(o1du)lug,(p.s.i. 23g 3g 7 .7 t e rs e ..wherem. R repre en s a a t.,a pha hydrocarbon T C. t%?tionelsti fl nessat10,000 -4 -s radical and R' represents an alkyl radical. Hardness 59 The invention also contemplatesthe use of other modifying ingredients such as pigments, fillers, brother com patible resins or plasticizers. With the addition of the proper pigments and fillers compositions of this nature would be suitable for cable sheathing, upholstery, wire insulation and the like. 7 V

The following examples will serve to illustrate the practice of the invention? 7 :Butyl N,N-bis(2-cyanoethyl)succinamate and a plasti- 5o 'sol grade vinyl chloride-acrylonitrile resin, containing 7 63.1% vinyl chloride and having a reduced viscosity in 1' .cyclohexanone of 1.33, were mixed together in a ratiosofm resin to plasticizer of 1:1. After milling one pass on a three roll mill a viscous plastisol was obtained.- The vis- 55 cosity, as measured with a Brookfieldsyiscosimeter at 6 7, rpm. with the #4 spindle at 27 C., was initially 18,000 .centipoises and at the end of seven days was 31,000 centi poises. At the end of :four weeks the viscosity was 50,500

centipoises." e A 40 gram portion was weighed into a beaker, de-

aerated by placing the beaker in a vacuum chamber, and 'then baked minutes at 325 C. A tough flexible plaque was obtained. a

0 V i H '55 EXAMPLE II Physical properiies bf atterson's; and has w Other batches of plastisol were prepared as in Example I. A portion was poured in a crystallizing dish,

.deaerated, and baked 20 minutes at 325YC. to give a tough, flexible sheet about 0.075 inch thick. Thin films day. W

Loss in 24 hours at 70 0., samples surrounded with activated carbon From the above figures it will be seen that the films had good tensile-elongation properties, good resistance to oil extraction, low volatility and fair resistance to water extraction.

Pieces from the 0.075 inch plaque were fluxed together on a two roll mill for five minutes at 190 C. and pressed at 140 C. and 1500 p.s.i. to give a tough, flexible sheet. The physical properties of this milled sheet, and of the plastisol plaque, were also determined with the following results:

From the figures shown above it can be seen that these sheets have good mechanical properties and fair low temperature characteristics.

EXAMPLE III Plasticized film cast from solution The following solutions were prepared:

Films were cast and allowed to air dry. After force drying at 200 F. to remove residual solvent clear, strong,

tough, flexiblefilms were obtained. The physical properties of the films were:

Film irom solution A B 0 Percent plasticizers on resin bssis.. 0 25 Mile thickness 2. 4 2. 9 2. 0

Avg. Elongation, Percent 6 27 176 Avg. Tensile Strength, p.s.i. 9, 640 6, 220 3, 840

EXAMPLE IV Plasticized organosols The following mixtures were ground in a one quart 13 pebble mill, containing 770 grams 05%" to it diameter flint pebbles, and rotating at 82 r.p.m.:

Resin Total Wt.

(gms) Hours ground Viscosity centistokes 2 Parlin Cup WOQDI 5""8" Q Or see

MCI

ass

ass

1 =optimum composition; Films were cast at 10 mils wet thickness on glass slides and baked 10 minutes at 350 F. Clear, strong films were obtained from all of the organosols and all but the last one were quite flexible.

Physical properties on the plasticized film from the optimum composition and from the unplasticized film were:

Thus it can be seen that the plasticizers can be incorporated into the standard organosols with the resulting increase in the flexibility of the films produced.

EXAMPLE V Properties of plasticized organosol films Organosol films containing varying amounts of butyl N,N-bis(2-cyanoethyl)succinamate were prepared by casting the organosol on glass slides and baking for 10 minutes at 350 F. Tensile and elongation data were obtained as follows:

Percent plasticizer on a a vinyl chloride-acrylpnitrile copolymer resin containing 60% vinyl chloride and 40% acrylomtrile basis 100 50 25 10 Thickness, mils 2. 5 1. 8 1. 6 1. 7 1. 7 Percent elongation. 382 292 20 6. 4 11 Tensile Strength 1, 766 3, 933 6, 890 11, 040 11, 922

It was further observed that the first film containing 100% plasticizer based on the resin weight, was very pliable and even showed rubber-like elasticity, described as snapbac and yet showed no sign of exudation.

EXAMPLE VI A sample of butyl N,N-bis(2-cyanoethyl)succinamate was mixed in three concentrations, 35%, 40% and 45% by weight of total compound, with a vinyl chlorideacrylonitrile copolyrner resin containing 60% vinyl 14 chloride and 40% acryionitrile and the resulting mixtures fiuxed on a two-roll mill at 135 C. Transparent flexible sheets, free of any indication of incompatibility, were obtained in each case. Samples from the milled sheets were compression molded into suitable test plaques at 150 C. The physical properties of the plaques were as follows: 1

Percent Plasticizer by weight 35 45 Tensile strength, p.s.i 3,650 3, 200 2, 800 Elongation, Percent 275 290 350 Load at elongation, p.s.i- 2, 450 1, 650 1, 000 ASTM stifiness modulus, p.s.i 3,600 1, 000 430 T4 G. (tortlonal stifi'ness of 10,000 p.s.i.) +21 +13. 5 +4 Flex Temperature (Tr) 0 +4 4. 5 -9. 5 Brittle Temperature, 0. +2 4 -11 Shore hardness 83 67 57 Percent Extraction:

O 1.2 2.0 2.5 Water 7. 7 1417 '19. 4 SPI Volatile-loss in 24 hrs. at 70 C 1. 3 1. 5 1. 5

Each composition contained 0.5% (on weight of total compound) of an organo-tin heat-stabilizer.

With the addition of the proper pigments, fillers, etc., compositions of this general range of flexibility would be suitable for cable sheathing, upholstery and wire'insul'ation.

*EXAMPLE VH Two samples of plasticized compositions were prepared by mixing dry resin Vinyon N, the plasticizer described in Example VI and an organo-tin stabilizer and fiuxed on a two-roll mill at C. Transparent, drysheets were obtained in each case. On the basis of an arbitrary criterion (a modulus of 1000 p.s.i. at 100% elongation) for a desired degree of room-temperature flexibility, the two samples performed as follows:

EXAMPLE VIII A plastisol plaque and a thin film, each based on equal parts of Vinyon N resin and Z-ethylbutyl N,N-bis(2- cyanoethyl) succinamate and prepared in the manner of Example I, had the following physical properties:

Tensile strength, p.s.i 1,775 Elongation, percent 325 Load at 100% elongation, p.s.i 950 ASTM Stifiness modulus, p.s.i 240 T C. (Flex temperature) 27.5 F C. (Tortional stifiness of 10,000 p.s.i.) 3 Brittle temperature, C. -3 Shore hardness 63 SP1 Volatile loss, percent 6.5 Sweat out None What is claimed is:

1. A polymerized vinyl chloride resin composition, containing at least 25 percent vinyl chloride polymerized therein, plasticized with a compound having the formula:

a compound. having the formula: V

wherein R represents a divalent, aliphatic hydrocarbon radical and R represents an alkyl radical containing from 1 through Scarbon atoms. 7 a

2. A composition of matter comprising an acrylonitrilevinyl chloride copolymer resin, containing at least 25 percent vinyl chloride polymerized therein, plasticized with methyl N,N-bis(2-cyanoethyl) succinamate.

3. A composition of matter comprising an acrylonitrilevinyl chloride copolymer resin, containing at least 25 percent vinyl chloride polymerized therein, plasticized with butyl N,N-bis(2-cyanoethyl) succinamate.

4. A composition of'matter comprising an acrylonitrilevinyl chloride copolymer resin, containing at least 25 percent vinyl chloride polymerized therein, plasticized 'with Z-ethylhexyl N,N-bis(2-cyanoethyl) succinamate.

5. A composition of matter comprising'an acrylonitn'le vinyl chloride copolymer resin containing at least 25 percent vinyl chloride polymerized therein, plasticized with butyl N,N-bis(2-cyanoethyl) glutaramate. i

6. A composition of matter comprising a vinyl chlorideacrylonitrilejcopolymer resin containing at least 25 percent vinyl chloride polymerized therein, plasticized with wherein R represents a divalent, aliphatic hydrocarbon radical and R' represents an alykyl radical containing from 1 through 8 carbon atoms.

7. A composition of matter comprising a vinyl chlorideacrylonitrile copolymer resin having a vinyl chloride con- 16 tent of ati least 25, percent polymerized therein, and containing an amount'of from about 5 percent to 60 percent by weight, based on the total composition, of a plasticizer having the formula:"

wherein R represents a divalent aliphatic hydrocarbon radical and R represents an alkyl radical containing from 1 through 8 carbon atoms.

8. -A composition of matter comprising a vinyl chlorideaerylonitrile copoylmer resin having a vinyl chloride content in the range of from about percent to 75 percent polymerized therein and containing an amount of from about 5 percent to percent by weight, based on the References Cited in the file of this patent V. UNITED WSTATESV PATENTS 2,426,728 DAlelio Sept. 2, 1941 2,750,401 Lynn June 12, 1956 2,790,820 Lynn Apr. 30, 1957 

1. A POLYMERIZED VINYL CHLORIDE RESIN COMPOSITION, CONTAINING AT LEAST 25 PERCENT VINYL CHLORIDE POLYMERIZED THEREIN, PLASTICIZED WITH A COMPOUND HAVING THE FORMULA: 